Cyanoalkyl ethers of polyhydric alcohols



Patented Mar. 16, 1948 CYANOALKYL ETHE RS OF POLYHYDRIC ALCOHOLS HermanA. Bruson, Rydal, Pa., assignor to The Resinous Products & ChemicalCompany, Philadelphia, Pa., a corporation of Delaware No Drawing.Original application January 15,

1941, Serial No. 374,603. Divided and this application December 29,1945, Serial No. 638,451 1 3 Claims. (Cl. 260-464) This inventionrelates to a method for preparing fl-cyanoalkyl ethers of polyhydricalcohols, having two to siX hydroxyl groups per molecule, of thealiphatic, arylaliphatic, and cycloaliphatic series and to the newcyanoalkyl ethers obtained thereby.

According to this invention, an alcohol having two to six (inclusive)hydroxyl groups per molecule, selected from a member of the aliphatic,arylaliphatic, or cycloaliphatic series, the chain of which may beinterrupted by oxygen or sulfur, is reacted in the presence of analkaline condensing agent or catalyst with at least one molecularequivalent of an c p-unsaturated open chain nitrile to form afi-cyanoalkyl ether of the polyhydric alcohol. Depending upon thequantity of the unsaturated nitrile used, one or more 13- cyanolalkylgroups may be introduced. The unsaturated nitriles which can be used areacrylonitrile and a-methyl-acrylonitrile compounds having the formulaCH2=C (R) CN wherein R is hydrogen or a methyl group.

The condensation takes place readily at temperatures between about C.and about 70 C. Since the reaction is exothermal, cooling at the startis often advantageous inorder to prevent undesired polymerization. Thequantity of alkaline catalyst used is small, an amount corresponding to0.5 to 2% on the weight of the polyhydric alcohol being sufilcient.Sodium methylate has been found to be very effective for the purpose,although sodium or potassium ethylate or metallic sodium or sodium oxidedissolved in the polyhydric alcohol itself can be used as the catalyst.There may also be used sodium hydroxide, potassium hydroxide, lime,barium hydroxide, quaternary ammonium hydroxides such as trimethylbenzyl ammonium hydroxide, etc., alkali metal amides, or the like. Thereaction may be carried out in the presence of an inert solvent orsuspending agent, particularly in those cases where one of thecomponents is a solid or is difilcultly soluble in the other reactant.For this purpose dioxane, benzene, toluene, dimethoxy tetraethyleneglycol, water, etc., are useful. a

Typical polyhydric alcohols oi the aliphatic, arylaliphatic, orcycloaliphatic series which may be used are as follows:

Ethylene glycol, or its homologues, including propylene, trimethylene,tetramethylene, pentamethylene, hexamethylene, octamethylene ordecamethylene glycols, 2,3-but-ylene glycol, 1,3-

butylene glycol, octadecane-diol, dlvlnyl glycol, dipropenyl glycol.glycerol, glyceryl-a-phenyl ether, glyceryl-a-methyl ether, trimethylolpropane 1,1,1, butantriol 1,2,3, pentaglycerol, erythritol,pentaerythrite, mannitol, sorbital, inositol, anhydroenneaheptite,diethylene glycol, dipropylene glycol, triethylene glycol, thlodiethylene glycol, thiotetraethylene glycol cyclohexanediols,1,2-dihydroxyethyl benzene, bis(fl-hydroxyethoxy)-benzene, xylyleneglycol, tetraethylene glycol, hexaethylene glycol, nonaethylene glycol,and the higher polyethylene glycols having molecular weights up to 4000.

One or more of the hydroxyl groups of the above compounds can beetherified by a fl-cyanoalkyl group to form usually well-definedcompounds useful in the plastic arts. These are also useful asintermediates in the preparation of polycarboxylic acids, esters, salts,amides, etc., which in turn are useful in diverse fields, includingresins, pharmaceuticals, and insecticides. The following are examplesillustrating this invention.

To 124 grams of anhydrous ethylene glycol, 4 grams of powdered sodiummethylate was added. The mixture was stirred and warmed to -'l0 C. forabout five minutes until a clear solution was obtained. The solution wascooled'to 15 C. and stirred while 212 grams of acrylonitrile was addeddropwise so that the temperature did not exceed 25 C. This required twoand onehalf hours. The mixture was then stirred at 25-28 C. for sixhours to complete the reaction. It was mixed with 200 cc. of water,neutralized with dilute hydrochloric acid, and extracted with 250 cc. ofethylene dichloride. The extract was distilled to recover the solvent,and the residual oil was fractionally distilled in vacuo. The mainfraction distilled under 2 mm. pressure at 156-166 C. (mostly 158 C./2mm.) as a colorless oil with a yield of 280 grams and corresponded tobis(2-cyan'oethoxy)ethane, a compound readily soluble in water or inbenzene.

To a solution of 10 grams of sodium methylate in 380 grams of propyleneglycol cooled to 20 C. there was added dropwise, while the mixture was'ethoxy) -propa ne-1,2 distilled between 160-170 C./12 mm. (mostly at1656-168 C./2 mm.) as a colorless oil. The yield was 710 grams.

To a solution of one gram of sodium methylate in 54 grams of2,3-butylene glycol cooled to 10 C., there was added dropwise 63.6 gramsof acrylonitrile while the mixture was stirred and maintained at atemperature between 10-20 C. The mixture was then stirred for six hourslonger at 20-25 C. and Poured into 150 cc. of saturated sodium chloridesolution. The oil which separated was distilled in vacuo. The desiredbis(pcyanoethoxy) -butane-2,3 distilled over at 165- 175 C./2 mm.(mostly 170 C./2 mm.) as a colorless oil which slowly solidified to awaxy crystalline mass with a yield oi 79 grams. Upon recrystallizationfrom alcohol-petroleum ether (1:1) mixture, the compound separated instout Prisms melting at 53-54 C,

To a solution of one gram of sodium methylate in 54 grams of1,3-butylene glycol, there was added dropwise at 25-40 C. 63.6 grams ofacrylonitrile during one hour and the mixture stirred for seven hours at25 C. There was then added 25 cc. of water and suflicient dilutehydrochloric acid to neutralize the alkalinity. The product was thenextracted with 100 cc. of ethylene dichloride and the extract distilledin vacuo. The bis(pcyanoethoxy) -butane-l,3 distilled at 170-175 C./1mm. as a colorless oil with a yield of 80 grams.

Esca mi le 4 NCCHzCHa-O-CHzCHzCHFO-CHzCHaCN To a solution of two gramsof sodium methylate in 76 grams of trimethylene glycol cooled to 20 C.,there was added dropwise 106 grams of acrylonitrile while the mixturewas stirred. During this time the temperature was held between 20 and 42C. The mixture was then stirred for six and one-half hours at 25 C.,poured into 100 cc. of water, neutralized with hydrochloric acid, andextracted with 150 cc. of ethylene dichloride. When the extract wasdistilled in vacuo, 159 grams of bis(B-cyanoethoxy) -propane-1,3 wasobtained as a colorless liquid boiling at 165170 C./1-2 mm.. moderatelysoluble in cold water and readily soluble in benzene.

Example 5 NC CHgcHr-o-CH:CHQCHiCHzCHg-O-CHgCHICN To a solution of onegram of sodium methylate in 46.5 grams of pentamethylene glycol, therewas added dropwise 47 grams of acrylonitrile while the mixture wasstirred. The temperature was held between 18 and 38 C. during theaddition, which required one hour. The mixture was then stirred for sixhours at 25 C., poured into 100 cc. oi water. and neutralized withhydrochloric acid. The oil layer was taken up in cc. of ethylenedichloride and this extract distilled in vacuo. Thedesired-bisQB-cyanoethoxy) pentane-1,5 distilled at 180-190 C./1-2 mm.as a pale yellow oil with a yield of 74 grams.

' Example 6 Fifty-two grams of decamethylene glycol, 50 cc. of dioxane,and 0.5 gram of sodium methylate were mixed and the mixture warmed to60-70 C. to give a clear solution which was cooled to 20 C., whereuponit became pasty. To this paste there was added dropwise during forty.

minutes 31.8 grams of acrylonitrile with good stirring while thetemperature was maintained between 20 and 25 C. The mixture was thenstirred for six hours at 25-30 C., during which time the pastedisappeared. The reaction prodnot was poured into 150 cc. of water andan oil layer separated, was washed with water, and then distilled invacuo. The product, corresponding in composition tobis(p-cyanoethoxy)-decane-1,10 distilled at 220-230 C./12 mm. as Icolorless oil.

JIHaCHzCN To a solution of 57.2 grams of 1,12-dihydroxyoctadecane in 75cc. of dioxane, 0.5 gram oi powdered sodium methylate was added and themixture heated to 70 C. until clear. The mixture was cooled to 45 C. and21.2 grams of acrylonitrile added dropwise during twenty minutes whilethe mixture was stirred and kept at a temperature of 4550 C. The mixturewas then stirred at 4045 C. for five and one-half hours, cooled,neutralized with dilute hydrochloric acid, 111- tered, and dried at 100c. under reduced pressure. The residue was dissolved in ethylenedichloride, washed with water, and the ethylene dichloride layerevaporated to dryness at 100 C. under reduced pressure. The residualoil, weighing 69 grams, solidified to a hard, white, waxy solid,corresponding by nitrogen analysis to the above formula.

Example 8 CHr-O-CHaOHaCN H-O-CHflHrCN Hz-O-CHrCHzCN Two grams of sodiummethylate was dissolved in 92 grams or pure glycerol at 60-70 C. Thesolution was cooled to 25 C. and stirred while 159 grams ofacrylonitrile was added dropwise thereto during the course of two andone-half hours while the temperature was maintained at 25-30 C. byexternal cooling. The mixture was stirred thereafter for six hours at 25C., then mixed with 100 cc. of water, neutralized with hydrochloric acidand extracted with cc. of ethylene dichloride. The extract was distilledunder reduced pressure after the solvent was removed. The desiredtris(p-cyanoethoxy)-propane-1,2,3 distilled over at 250-260 C. under 12mm. pressure as a pale yellow oil with a yield of 186 grams.

Example 9 QOTCHPZH-O-CHICHICN To a solution of 84 grams oiglyceryl-a-phenyl ether in 100 cc. of dioxane, one gram of powderedsodium methylate was added and the mixture stirred and heated to 70 C.until clear. It was then cooled to 19 C. and 53 grams of acrylonitrileadded dropwise during forty minutes while the mixture was stirred andmaintained at a temperature between 20 and 25 C. It was then stirred forseven hours more at 25-50 C., neutralized with dilute hydrochloric acid,filtered, and the filtrate evaporated under reduced pressure on a steambath. The residual oil was washed with water and distilled in vacuo. Thedesired product came over between 235 and 250 C. at 1 mm. as a colorlessoil in a yield of 80 grams.

Example n-o-cmcmcrr dm-o-omcmon To a solution of two grams of sodiummethylate in 106 grams of glyceryl-a-methyl ether, there was addeddropwise with stirring and cooling to 2530 C. 106 grams of acrylonitrileduring the course of one hour. The mixture was then stirred for six andone-half hours at 25-30 C. to complete the reaction. The product wasmixed with 25 cc. of water, neutralized with 10% hydrochloric acid, andextracted with 100 cc. of ethylene dichloride. Upon distillation of theextract in vacuo, there was obtained 131 grams of 2,3-bis-(p-cyanoethoxy) -1-methoxypropane as a colorless liquid boiling between190 and 198 C. at 1-2 mm.

(b) In the same manner, a solution of one gram of sodium methylate in 74grams of glyceryi-a-n-butyl ether was reacted with 53 grams ofacrylonitrile to yield 55 grams of 2,3-di( B-cyanoethoxy)-1-n-butoXy-propane:

a colorless liquid boiling at 200 C./1 mm.

Example 11 tilled in high vacuo. The desired bis(B-cyanoethoxy) -diethylether boiled at 185l95 C./12 mm. as a colorless oil. It is very solublein water. The yield was 9'? grams, which corresponds to a 91% yield.

To a solution of two grams of sodium methylate in 134 grams ofdipropylene glycol, there was added 106 grams of acrylonitrile dropwiseduring one hour while the solution was stirred and cooled. Thetemperature during the addition was beone and one-half hours.

tween 25 and 45 C. The mixture was then stirred at 25 C. for seventeenhours, poured into cc. of water, neutralized with dilute hydrochloricacid, and extracted with 100 cc. of ethylene dichloride. Upon distillingthe extract in vacuo, the desired bisQS-cyanoethoxy)-2-2'-dipropyl etherdistilled over at 185-195 C. /1-2 mm. as a colorless, water-solubleliquid with a yield of 175 grams.

Example 13 To a solution of two grams or sodium methylate in 150 gramsof triethylene glycol, there was added dropwise, with stirring, 106grams of acrylonitrile. The temperature was held between 20 and 30 C.during the addition, which required The mixture was then stirred forsixteen hours at 25 C., diluted with 50 cc. of water, and neutralizedwith hydrochloric acid. The product was extracted by shaking withethylene dichloride and the extract distilled under reduced pressure.The desired bis(fl-cyanoethoxyethyl) ether of ethylene glycol distilledover at 210-220 C./1-2 mm. as a pale yellow, water-soluble liquid in ayield of 198 grams.

(b) By using 194 grams of tetraethylene glycol in place of thetriethylene glycol in the above procedure, there was obtained thebis(,B-cyanoethyl) ether of tetraethylene glycol having the formula:

It distilled at 220-230 C./1-2 mm. as a pale yellow oil in a yield of184 grams.

Example 14 One gram of powdered sodium methylate was dissolved at 60-70C. in 141 grams of hexaethylene glycol, HOC2H4-(OC2H4) 4OC2H4OH. Thesolution was cooled to 15 C. and 53 grams of acrylonitrile addeddropwise thereto while the mixture was stirred and maintained at atemperature of 20-28 C. The mixture was then stirred for seventeen hoursat 25 0., mixed with 25 cc. of water, neutralized with dilutehydrochloric acid, and extracted with 100 cc. of ethylene dichloride.The extract was dried in high vacuo at 100 0., giving a residue of anambercolored oil in a yield of 181 grams. This residue was found bynitrogen analysis to correspond to the above formula (N found, 7.10%;theory 7.22%).

Example 15 One-half gram of sodium methylate was dissolved at 70 C. in asolution of 200 cc. of dioxane and grams of polyethylene glycol,

perature during the addition remained at 30 C."

The mixture was then stirred for five hours at 30 and at 40-50' C. fortwo hours. It was then cooled, neutralized with dilute hydrochloricacid, filtered, and the filtrate evaporated in vacuo on a steam bath toremove the dioxane. There remained 124 grams of a pale oil, which wasdissolved in 100 cc. of ethylene dichloride. This solution was shakenwith 25 cc. of water, the ethylene dichloride layer separated therefromand evaporated in vacuo on a steam bath. The residual product consistedof 113 grams of a pale, hard wax having on analysis 0.90% nitrogen. Theproduct, therefore, has the average composition: NCCH2CH2OCH2CHz-(OCH2CH2) 5o- OCH2CH2OCH2CH2CN It is readily soluble inwater or benzene.

To a solution of two grams of sodium ethylate in 122 grams ofthiodiethylene glycol,

cooled to 20 C. there was added dropwise 106 grams of acrylonitrileWhile the mixture was cooled and stirred. During the addition, whichrequired one hour, the temperature was maintained between 20 and 50 C.by external cooling. The mixture was then stirred for seven hours at 25C., poured into 100 cc. of water, neutralized with hydrochloric acid,and taken up in 100 cc. of ethylene dichloride. The product wasrecovered from the ethylene dichloride layer by distillation in vacuo.The bis(fi-cyanoethoxy)-diethyl sulfide distilled over at 220-230 C./1-2mm. as a pale yellow oil in a yield of 210.5 grams, or 92% of theory.

It is soluble in benzene, somewhat soluble in cold water, and insolublein petroleum naphtha.

Example 17 To a solution of 0.6 gram of sodium methylate in 31.8 gramsof diethylene glycol there was added 41 grams of methacrylonitrile. Themixture was stirred for twenty-one hours at 25-30 C. and then was heatedat 65-70 C. for five hours. It was cooled, neutralized with hydrochloricacid, and distilled in vacuo. After a forcrun of unchanged reactants hadcome over. the main fraction distilled over between 150 and 175 C./2 mm.On fractionation, it yielded 19 grams of colorless oil boiling at150-155 C./1 mm. and having the formula:

OH: H O CHzCHr-O-CHzCHz-O-CIIr-H-CN Example 18 (a) xccHmm-o-mo CHPOCH:CH:CN

c a ccmcm-o-rno cm-o-cmomcrr To a suspension of 40.8 grams of drypentaerythrite (ground to pass a 100 mesh sieve) in 100 cc. of anhydrousdioxane there was added two grams of powdered sodium methylate. Themixture was stirred at 25-30 C. for fifteen hours. Sixty-three andsix-tenth grams of acrylonitrile was then added during five minutes andthe mixture stirred for forty-eight hours at 25- 30 C. It was thenheated at 50-60 C. for eight hours, cooled, and filtered. The filtratewas heated in vacuo on a steam bath and evaporated to dryness. There wasthus obtained 46 grams of an amber-colored syrup which was filtered toremove traces of polymer and pentaerytIn-ite. The product contained byanalysis 15.8% nitrogen, which agrees well with the value 16.09%calculated tor tetra-(p-cyanoethoxymethyl) -methane. The product isreadily soluble in dioxane.

(b) Acrylonitrile (63.6 grams) was added to a stirred mixture of 40.8grams oi pentaerythrite, 50 cc. of water, and two grams or sodium hydroxide at 25 C. The mixture was then warmed and stirred for seven hoursat 40-50 C. and allowed to stand for twenty-four hours at roomtemperature. The alkalinity was then neutralized with dilutehydrochloric acid (10% strength) and the oil layer separated. It waswashed once with 300 cc. of cold water and then dried under reducedpressure at -95 C. The residual product was a colorless syrup weighing83 grams. It was very soluble in acetone, chloroform, or methanol andappreciably soluble in water. Its analysis showed it to consist to theextent of at least of tetra (cyanoethoxymethyl) -methane:

C (CHzOCHzCHzCN) 4 (c) In the above examples pentaerythrite has beenshown as a separately prepared starting material. The reaction may beperformed essentially as above, however, without separation of thepentaerythrite. This is accomplished by reacting formaldehyde,acetaldehyde, and lime in solution and, without separation of theproduct, adding acrylonitrile or methacrylonitrile.

Example 19 (CHzhC-CHz-O-CHnCHaCN To a solution of 90 grams ofisobutylene glycol and two grams of sodium methylate, there was addedduring one hour, dropwise, 53 grams of acrylonitrile while the mixturewas stirred and maintained at a temperature between 23 and 35 C. Thismixture was stirred for five and one-half hours at 25 0., then mixedwith 25 cc. of water, neutralized with dilute hydrochloric acid, andextracted with cc. of ethylene dichloride. The extract was distilledunder reduced pressure to give a. yield of 102 grams of the desiredp-cyanoethoxy-tertiary butanol, distilling at 126-130 C./10 mm. as acolorless oil. It is readily soluble in water.

(b) In the same manner, 118 grams of 2- methyl-2,4-pentanediol, twograms of sodium methylate, and 53 grams of acrylonitrile yielded 100grams of acolorless oil boiling at -l20 C./1-2 mm. and having theformula:

CH: CH: cape-cmn-o-cnicmcn 9 dilute hydrochloric acid, filtered, dilutedwith 18 cc. oi water, and shaken with 100 cc. of ethylene dichloride.The extract was distilled under reduced pressure, yielding 40 grams of aproduct distilling between 180 and 190 C. at 1 mm. as a colorless oil.

Example 21 (a) Acrylonitrile (63.6 grams) was added to a solutionconsisting of 36.4 grams of mannitol, 100 cc. of water. and two grams ofsodium nydroxide. The mixture was stirred at 40-50' C. for five hours,then cooled and neutralized with dilute hydrochloric acid. The clearsolution was evaporated to dryness in vacuo on a steambath at 90-95" 0.,giving a residue weighing 100 grams. This was dissolved in ethylenedichloride and illtcred to remove sodium chloride. The clear filtratewas then evaporated to dryness in vacuo on a steam bath to yield aproduct obtained as an almost colorless syrup, soluble in methanol oracetone, consisting essentially of the hexa-(cyanoethoxy) -hexane:

CHr-O-CHrCHsCN (EH-O-CHsCHrCN) tm-o-cmcmcn 4 (b) Inositol in equivalentamount may be substituted for mannitol in the above example and reactedin the same manner to give a colorless syrup which consists essentiallyof hexa-(fl-cyanoethoxy) cyclohexane.

Example 22 NC CHICHPO-CHICHIOC HaCHr-O-CHsCHaCN 10 vacuo to removewater, filtered from salt, and the clear, colorless filtrate distilledin high vacuo. The desired bis-(s-cyanoethoxy)-diethyl ether boiled at185-195 C./1-2 mm. as a colorless oil.

5 It is very soluble in water. The yield was 98 grams, which correspondsto a 92% yield.

The present application is a division of United States applicationSerial No. 374,603, filed January 15, 1941, now abandoned. The subjectmatter claimed in the present application is directed to compounds ofthe formula:

NCCHzCHzO-AOCH2CH2CN wherein A is an alkylene group having at least twocarbon atoms between oxygen atoms. containing from ten to eighteencarbon atoms, inclusive. These new compounds form a class of uniqueplasticizers.

I claim:

1. Compounds of the formula:

wherein A is an alkylene group having ten to twelve carbon atoms betweenoxygen atoms and containing from ten to eighteen carbon atoms,

inclusive.

2. As a new compound, bis(p-cyanoethoxy)- decane-l,10.

3. As a new compound, bis(p-cyanoethoxy)- so octadecane-1,12.

HERMAN A. BRUSON.

REFERENCES CITED The following references are of record in the Y file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,359,708 Bruson Oct. 3, 19442,388,813 Allen et a1 NOV. 13, 1945 2,404,164 Carpenter July 16, 1946OTHER REFERENCES Bruson et al., Jour. Am. Chem. 800., vol. 65, 5 pages23-27 (1943).

11 I i I 12 Certificate of Correction Patent No. 2,437,905. March 16,1948. HERMAN A. BRUSON It is hereby certified that errors appear in theprinted specification of the above numbered patent re uinng correctionas follows: Column 2, line 5, for the word sorbital read aorbito column9, hnes 24 to 28, Example 21, for the formula reading OH O OH OH,0OHa-O-OHaOHaON n-o-omomoN d n-o-omomum. Hz-O-UHaUHsUN 4 Hr-O-OHzCHaONand that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Ofiice.

Signed and sealed this 18th day of May, A. D. 1948.

THOMAS F. MURPHY,

Am'atant Oom/miasioner of Patents.

